CN102212309B - Method for preparing unsaturated polyester polyurethane block copolymer solventless coating - Google Patents
Method for preparing unsaturated polyester polyurethane block copolymer solventless coating Download PDFInfo
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Abstract
The invention provides a method for preparing an unsaturated polyester polyurethane block copolymer solventless coating. The method comprises the following steps of: performing polycondensation step by step by using diatomic alcohol, maleic anhydrides and phthalic anhydridr to obtain hydroxide terminated unsaturated polyester oligomers; performing step-by-step polyaddition by using the unsaturated oligomers, diisocyanate and polyethylene glycol to obtain solution of isocyanate terminated unsaturated polyester polyurethane block prepolymers in the presence of styrene serving as a solvent; end-capping the prepolymers by beta-hydroxyethyl methacrylate to obtain base materials of hydroxide terminated unsaturated polyester polyurethane block active prepolymers; and mixing the base materials, pigments, fillers and a redox initiator to obtain the unsaturated polyester polyurethane block copolymer solventless coating.
Description
Technical field
The present invention relates to a kind of preparation method of coating.
Background technology
Along with the enhancing of mankind's environmental consciousness and the enforcement of countries in the world environmental regulation, the modern coatings industry has formed the environmentally friendly mainstream development direction of Water-borne modification, photocuring and solvent free.The solvent free of coating refers to that each component of coating all forms coating and non-volatile loss after paint solidification, can realize the zero VOC discharging of coating, does not form the Prevent Carbon Contamination of environment, belongs to the main Types of environmentally friendly coating.solventless coatings is before curing, for guaranteeing preparation and the workability of coating, from form, similar with solvent based coating, belong to the polymer compound fluid, when difference is that solventless coatings solidifies, interact by physics or chemical mode between all components in coating and jointly form coating composite material, and non-volatile component, for reaching this purpose, in Design of Coatings Formulation, must take into full account the interaction between each component, instrumental analysis from coating composition, only have as forming coated material by chemical action between the solvent of adjusting the paint flow sex change and coating master film-forming resin, just can effectively reduce the discharging of organic solvent, just might realize zero VOC discharging, therefore, solventless coatings is in formulating of recipe, the reaction compatibility of seeking solvent and resin is the core of coating solvent free research.Unremitting effort through the coating scientific worker, obtaining certain progress aspect the coating solvent free, at present, high solid coating has reduced the organic solvent of coating system significantly, low VOC coatings enters the application stage, but such coating still can't be realized zero VOC discharging, and the research of solventless coatings still needs long-term and unremitting effort; The solventless coatings that forms with unsaturated polyester and unsaturated solvent (reactive thinner) is one of important kind of numerous solventless coatingss, but its widespread uses of restriction such as its cure shrinkage is large, coating is easy to crack, attachment fastness is low, poor impact toughness.
Unsaturated polyester resin (UPR) is recent domestic development one of thermosetting resin comparatively rapidly.Yet UPR is hard and crisp after solidifying, and impact property is poor, and the shortcomings such as cure shrinkage high (general cure shrinkage is 7%～8%) restrict its widespread use.At present, the modification for UPR mainly concentrates on two aspects of its toughening modifying and low contraction modification.In order to improve the shock resistance of UPR goods, often need UPR to carry out the toughness modification.From introducing the macromole flexible chain, the mobility that increases crosslinked network chain is considered, introduces soft segment when synthetic UPR, can effectively improve fragility, but the too much soft segment that adds, after UPR can cause resin solidification, physical strength descends.Development in recent years a kind of method of modifying faster based on second-phase elastic properties of materials body to the UPR toughening modifying.What elastic body toughening was commonly used is that fluid rubber is toughness reinforcing.Due to the high-flexibility of rubber phase, significantly improved the toughness of UP, though rubber elastomer can increase substantially shock strength, stretching, flexural strength, resistance toheat descend to some extent.
At present, the low contraction modification for UPR is mainly to reduce its cure shrinkage by adding thermoplasticity shrinking agent (LPA).Shrinking agent commonly used has polystyrene, polymethylmethacrylate and dially phthalate etc., has also developed polycaprolactone, modified polyurethane and cellulose acetate butyl ester etc.Adopt the LPA modification can improve the fragility of UPR, reduce cure shrinkage, improve shock strength, but can reduce the tensile strength of UPR.
Urethane has high-flexibility as the extraordinary elastomerics of a kind of property reconciled, and both are in conjunction with maximizing favourable factors and minimizing unfavourable ones, and performance advantage has separately not only reduced cure shrinkage, has also increased toughness.All the time, people concentrate on by adding polyurethane elastomer and UPR physical blending reaching the purpose of modification for the modification of UPR, but have often also reduced other mechanical property when improving its impelling strength, reduction cure shrinkage.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of unsaturated polyester block polymers of polyurethane solventless coatings.
The present invention is the preparation method of unsaturated polyester block polymers of polyurethane solventless coatings, the steps include:
synthesizing of step (1) terminal hydroxy group unsaturated polyester ester oligomer: the suitable dibasic acid anhydride that will measure, ethylene glycol, dimethylbenzene, the vitriol oil adds successively electric stirring is housed, water trap, thermometer, in the reaction vessel of electric mantle heating, it is saturated acid anhydrides that dibasic acid anhydride adopts phthalic anhydride, MALEIC ANHYDRIDE is unsaturated acid anhydride, the mol ratio of phthalic anhydride and cis-butenedioic anhydride is 2～3: 1, be heated to start stirring after dissolution of solid, and be warming up to 150 ℃, reacted 2 hours, be warming up to 190+2 ℃ of reaction 1 hour, be cooled to 150 ℃ and add the dibasic alcohol that measures, being evacuated to hydroxyl value meets the requirements, steam solvent, when being cooled to below 50 ℃, resin adds vinylbenzene, stir, filter discharging, keep in Dark Place, hydroxyl molar excess percentage ratio is 20%～100%, the oligopolymer number-average molecular weight is 500～2000,
the preparation of step (2) unsaturated polyester block polymers of polyurethane base-material: the terminal hydroxy group unsaturated polyester ester oligomer UPR styrene solution of first step (1) being synthesized, vulcabond and dibutyl tin laurate add electric stirring are housed, condenser, thermometer, in the reaction vessel of electric mantle heating, be warming up to 60 ℃ of insulation reaction, system-NCO% processed, it is the isocyanate group content constant, add polyoxyethylene glycol carry out block reaction to-NCO% is constant, to polymerization system add the end-capping reagent that measures carry out end capping to system-NCO% equals at 0 o'clock, stopped heating, adjust viscosity with reactive thinner qualified, stop stirring, filter discharging, keep in Dark Place,
The preparation of step (3) unsaturated polyester block polymers of polyurethane coating: accurately take unsaturated polyester block polymers of polyurethane base-material, pigment and filler by formula ratio, mix in container, after stirring, pour into and be dispersed to fineness 40 μ m in sand mill, add auxiliary agent and initiator oxidation component to stir evenly, adjust viscosity to qualified discharging as coating first component take reactive thinner, it is the second component that the initiator reduction components is dissolved in reactive thinner; First, second component accurate-metering mixes, the brushing model, and Air drying 0.5 hour detects the coating property indices.
The present invention adopts dibasic alcohol, MALEIC ANHYDRIDE and phthalic anhydride to generate terminal hydroxy group unsaturated polyester ester oligomer by Step Condensation; Unsaturated oligopolymer and vulcabond, polyoxyethylene glycol generate the unsaturated polyester polyurethane blocks pre-polymer solution of terminal isocyanate groups through addition polymerization progressively take vinylbenzene as solvent; Prepolymer obtains alkene end group unsaturated polyester polyurethane blocks active prepolymer base-material with the Hydroxyethyl acrylate end-blocking; The composite preparation solventless unsaturated polyester of active prepolymer base-material and color stuffing and redox initiator block polymers of polyurethane solventless coatings.This coating has zero VOC discharging, without Prevent Carbon Contamination, environmental friendliness, normal temperature solidified, cure shrinkage is low, the coating attachment fastness is high, impelling strength good.
Embodiment
The present invention is the preparation method of unsaturated polyester block polymers of polyurethane solventless coatings, the steps include:
synthesizing of step (1) terminal hydroxy group unsaturated polyester ester oligomer: the suitable dibasic acid anhydride that will measure, ethylene glycol, dimethylbenzene, the vitriol oil adds successively electric stirring is housed, water trap, thermometer, in the reaction vessel of electric mantle heating, it is saturated acid anhydrides that dibasic acid anhydride adopts phthalic anhydride, MALEIC ANHYDRIDE is unsaturated acid anhydride, the mol ratio of phthalic anhydride and cis-butenedioic anhydride is 2～3: 1, be heated to start stirring after dissolution of solid, and be warming up to 150 ℃, reacted 2 hours, be warming up to 190 ± 2 ℃ of reactions 1 hour, be cooled to 150 ℃ and add the dibasic alcohol that measures, being evacuated to hydroxyl value meets the requirements, steam solvent, when being cooled to below 50 ℃, resin adds vinylbenzene, stir, filter discharging, keep in Dark Place, hydroxyl molar excess percentage ratio is 20%～100%, the oligopolymer number-average molecular weight is 500～2000,
the preparation of step (2) unsaturated polyester block polymers of polyurethane base-material: the terminal hydroxy group unsaturated polyester ester oligomer UPR styrene solution of first step (1) being synthesized, vulcabond and dibutyl tin laurate add electric stirring are housed, condenser, thermometer, in the reaction vessel of electric mantle heating, be warming up to 60 ℃ of insulation reaction, system-NCO% processed, it is the isocyanate group content constant, add polyoxyethylene glycol carry out block reaction to-NCO% is constant, to polymerization system add the end-capping reagent that measures carry out end capping to system-NCO% equals at 0 o'clock, stopped heating, adjust viscosity with reactive thinner qualified, stop stirring, filter discharging, keep in Dark Place,
The preparation of step (3) unsaturated polyester block polymers of polyurethane coating: accurately take unsaturated polyester block polymers of polyurethane base-material, pigment and filler by formula ratio, mix in container, after stirring, pour into and be dispersed to fineness 40 μ m in sand mill, add auxiliary agent and initiator oxidation component to stir evenly, adjust viscosity to qualified discharging as coating first component take reactive thinner, it is the second component that the initiator reduction components is dissolved in reactive thinner; First, second component accurate-metering mixes, the brushing model, and Air drying 05 hour detects the coating property indices.
When the unsaturated polyester block polymers of polyurethane base-material of the above step (2) prepared, hydroxy component was comprised of terminal hydroxy group unsaturated polyester ester oligomer and polyoxyethylene glycol, and both mol ratio is 1: 2～1; The polymerization degree of polyoxyethylene glycol is 5～10.
When the unsaturated polyester block polymers of polyurethane of the above step (2) prepared, vulcabond was tolylene diisocyanate, and isocyanate group molar excess percentage ratio is 50%～100%, and the segmented copolymer number-average molecular weight is 2500～5000.
When the unsaturated polyester block polymers of polyurethane base-material of the above step (2) prepared, end-capping reagent was methacrylic acid-β hydroxyl ethyl ester, and its consumption is 1.2～1.5 times of diisocyanate based molar excess number.
When the unsaturated polyester block polymers of polyurethane solventless coatings of the above step (3) prepared, base-material, pigment and filler accounted for respectively 65%～80%, 9%～16%, 10%～18% of coating first component formula total mass.
When the unsaturated polyester block polymers of polyurethane solventless coatings of the above step (3) prepares, auxiliary agent comprises solidifying agent dibenzoyl peroxide, defoamer organic silicon acrylic ester, anti-wear agent paraffin and stablizer para benzoquinone, and consumption accounts for respectively 0.6%, 0.2%, 0.1% and 0.1% of coating first component formula total mass.
When unsaturated polyester block polymers of polyurethane solventless coatings prepared in the above step (3), coating second component was the reactive thinner solution of curing catalyst DMA, and mass concentration is 10%.
When the unsaturated polyester block polymers of polyurethane solventless coatings of the above step (3) prepared, reactive thinner was comprised of methyl methacrylate and butyl acrylate, and both mass ratio is 2～1: 1.
The present invention adopts two-component coating, and the construction quality ratio of first, second component is 10: 1, and the curing environment temperature is not less than 20 ℃, 0.5 hour set time.
The present invention adopts the chemical equation statement, the steps include:
Synthesizing of step (1) terminal hydroxy group unsaturated polyester ester oligomer:
The preparation of step (2) unsaturated polyester block polymers of polyurethane base-material:
The preparation of step (3) unsaturated polyester block polymers of polyurethane coating.
The preparation method of unsaturated polyester block polymers of polyurethane solventless coatings the steps include:
synthesizing of step (1) terminal hydroxy group unsaturated polyester ester oligomer: the suitable dibasic acid anhydride that will measure, ethylene glycol, dimethylbenzene, the vitriol oil adds successively electric stirring is housed, water trap, thermometer, in the reaction vessel of electric mantle heating, it is saturated acid anhydrides that dibasic acid anhydride adopts phthalic anhydride, MALEIC ANHYDRIDE is unsaturated acid anhydride, the mol ratio of phthalic anhydride and cis-butenedioic anhydride is 2～3: 1, be heated to start stirring after dissolution of solid, and be warming up to 150 ℃, reacted 2 hours, be warming up to 190+2 ℃ of reaction 1 hour, be cooled to 150 ℃ and add the dibasic alcohol that measures, being evacuated to hydroxyl value meets the requirements, steam solvent, when being cooled to below 50 ℃, resin adds vinylbenzene, stir, filter discharging, keep in Dark Place, hydroxyl molar excess percentage ratio is 20%～100%, the oligopolymer number-average molecular weight is 500～2000,
the preparation of step (2) unsaturated polyester block polymers of polyurethane base-material: the terminal hydroxy group unsaturated polyester ester oligomer UPR styrene solution of first step (1) being synthesized, vulcabond and dibutyl tin laurate add electric stirring are housed, condenser, thermometer, in the reaction vessel of electric mantle heating, be warming up to 60 ℃ of insulation reaction, system-NCO% processed, it is the isocyanate group content constant, add polyoxyethylene glycol carry out block reaction to-NCO% is constant, to polymerization system add the end-capping reagent that measures carry out end capping to system-NCO% equals at 0 o'clock, stopped heating, adjust viscosity with reactive thinner qualified, stop stirring, filter discharging, keep in Dark Place,
The preparation of step (3) unsaturated polyester block polymers of polyurethane coating: accurately take unsaturated polyester block polymers of polyurethane base-material, pigment and filler by formula ratio, mix in container, after stirring, pour into and be dispersed to fineness 40 μ m in sand mill, add auxiliary agent and initiator oxidation component to stir evenly, adjust viscosity to qualified discharging as coating first component take reactive thinner, it is the second component that the initiator reduction components is dissolved in reactive thinner; First, second component accurate-metering mixes, the brushing model, and Air drying 0.5 hour detects the coating property indices.
The below further launches the present invention with embodiment more specifically.
(1) terminal hydroxy group unsaturated polyester ester oligomer is synthetic
With the 24.8g MALEIC ANHYDRIDE, 177.6g Tetra hydro Phthalic anhydride, 123.8g ethylene glycol and the 50g dimethylbenzene 2g vitriol oil add in the reaction vessel that electric stirring, water trap, thermometer, electric mantle heating are housed successively, be heated to start stirring after dissolution of solid, and be warming up to 150 ℃, reacted 2 hours, be warming up to 190 ± 2 ℃ of reactions 1 hour, be cooled to 150 ℃ and add 25g ethylene glycol, be evacuated to hydroxyl value and meet the requirements, steam dimethylbenzene, when being cooled to below 50 ℃, resin adds 100g vinylbenzene, stir, discharging is standby, keeps in Dark Place.
(2) the unsaturated polyester block polymers of polyurethane is synthetic
With 208.2g terminal hydroxy group unsaturated polyester ester oligomer styrene solution, 97.4g tolylene diisocyanate and 4g dibutyl tin laurate add in the reaction vessel that electric stirring, condenser, thermometer, electric mantle heating are housed, be warming up to 60 ℃ of insulation reaction, to system-NCO%, it is the isocyanate group content constant, add the 86.2g polyoxyethylene glycol to carry out block reaction constant to system-NCO%, add 50g methacrylic acid-β hydroxyl ethyl ester react to system-NCO% equals at 0 o'clock, stopped reaction, discharging is standby, keeps in Dark Place.
(3) preparation of unsaturated polyester block polymers of polyurethane solventless coatings
Press the accurate base-material of table 1 formula, pigment, calcene filler, and mix in container, after stirring, pour into and be dispersed to fineness 40 μ m in sand mill, add auxiliary agent to stir evenly, adjust viscosity to qualified discharging as coating first component take reactive thinner; Curing catalyst is dissolved in reactive thinner, and being formulated as 10% solution is the second component; First, second component mixes in the ratio of 10: 1, the sample preparation of spray plate, and Air drying 2 hours detects coating property indices, test item and result such as table 2.
Table 1 unsaturated polyester block polymers of polyurethane solventless coatings formula table
Table 2: unsaturated polyester block polymers of polyurethane solventless coatings detects table
Claims (7)
1. the preparation method of unsaturated polyester block polymers of polyurethane solventless coatings, the steps include:
synthesizing of step (1) terminal hydroxy group unsaturated polyester ester oligomer: the suitable dibasic acid anhydride that will measure, ethylene glycol, dimethylbenzene, the vitriol oil adds successively electric stirring is housed, water trap, thermometer, in the reaction vessel of electric mantle heating, it is saturated acid anhydrides that dibasic acid anhydride adopts phthalic anhydride, MALEIC ANHYDRIDE is unsaturated acid anhydride, the mol ratio of phthalic anhydride and cis-butenedioic anhydride is 2～3: 1, be heated to start stirring after dissolution of solid, and be warming up to 150 ℃, reacted 2 hours, be warming up to 190 ± 2 ℃ of reactions 1 hour, be cooled to 150 ℃ and add the dibasic alcohol that measures, being evacuated to hydroxyl value meets the requirements, steam solvent, when being cooled to below 50 ℃, resin adds vinylbenzene, stir, filter discharging, keep in Dark Place, hydroxyl molar excess percentage ratio is 20%～100%, the oligopolymer number-average molecular weight is 500～2000,
the preparation of step (2) unsaturated polyester block polymers of polyurethane base-material: the terminal hydroxy group unsaturated polyester ester oligomer UPR styrene solution of first step (1) being synthesized, vulcabond and dibutyl tin laurate add electric stirring are housed, condenser, thermometer, in the reaction vessel of electric mantle heating, be warming up to 60 ℃ of insulation reaction, system-NCO% processed, it is the isocyanate group content constant, add polyoxyethylene glycol carry out block reaction to-NCO% is constant, to polymerization system add the end-capping reagent that measures carry out end capping to system-NCO% equals at 0 o'clock, stopped heating, adjust viscosity with reactive thinner qualified, stop stirring, filter discharging, keep in Dark Place, when the unsaturated polyester block polymers of polyurethane prepared, vulcabond was tolylene diisocyanate, and isocyanate group molar excess percentage ratio is 50%～100%, and the segmented copolymer number-average molecular weight is 2500～5000,
The preparation of step (3) unsaturated polyester block polymers of polyurethane coating: accurately take unsaturated polyester block polymers of polyurethane base-material, pigment and filler by formula ratio, mix in container, after stirring, pour into and be dispersed to fineness 40 μ m in sand mill, add auxiliary agent and initiator oxidation component to stir evenly, adjust viscosity to qualified discharging as coating first component take reactive thinner, it is the second component that the initiator reduction components is dissolved in reactive thinner; First, second component accurate-metering mixes, the brushing model, and Air drying 0.5 hour detects the coating property indices; When unsaturated polyester block polymers of polyurethane solventless coatings prepared, base-material, pigment and filler accounted for respectively 65%～80%, 9%～16%, 10%～18% of coating first component formula total mass.
2. the preparation method of unsaturated polyester block polymers of polyurethane solventless coatings according to claim 1, it is characterized in that: when the unsaturated polyester block polymers of polyurethane base-material of step (2) prepares, hydroxy component is comprised of terminal hydroxy group unsaturated polyester ester oligomer and polyoxyethylene glycol, and both mol ratio is 1: 2～1; The polymerization degree of polyoxyethylene glycol is 5～10.
3. the preparation method of unsaturated polyester block polymers of polyurethane solventless coatings according to claim 1, it is characterized in that: when the unsaturated polyester block polymers of polyurethane base-material of step (2) prepares, end-capping reagent is methacrylic acid-β hydroxyl ethyl ester, and its consumption is 1.2～1.5 times of diisocyanate based molar excess number.
4. the preparation method of unsaturated polyester block polymers of polyurethane solventless coatings according to claim 1, it is characterized in that: when the unsaturated polyester block polymers of polyurethane solventless coatings of step (3) prepares, auxiliary agent comprises solidifying agent dibenzoyl peroxide, defoamer organic silicon acrylic ester, anti-wear agent paraffin and stablizer para benzoquinone, and consumption accounts for respectively 0.6%, 0.2%, 0.1% and 0.1% of coating first component formula total mass.
5. the preparation method of unsaturated polyester block polymers of polyurethane solventless coatings according to claim 1, it is characterized in that: when unsaturated polyester block polymers of polyurethane solventless coatings prepares in step (3), coating second component is curing catalyst N, the reactive thinner solution of accelerine, mass concentration are 10%.
6. the preparation method of unsaturated polyester block polymers of polyurethane solventless coatings according to claim 1, it is characterized in that: when the unsaturated polyester block polymers of polyurethane solventless coatings of step (3) prepares, reactive thinner is comprised of methyl methacrylate and butyl acrylate, and both mass ratio is 2～1: 1.
7. the preparation method of unsaturated polyester block polymers of polyurethane solventless coatings according to claim 1, it is characterized in that: adopt two-component coating, the construction quality ratio of first, second component is 10: 1, and the curing environment temperature is not less than 20 ℃, 0.5 hour set time.
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| CN102559039B (en) * | 2011-12-29 | 2013-12-11 | 中昊北方涂料工业研究设计院有限公司 | Preparation method of high-cross-linked UV (ultraviolet) curing aqueous polyurethane paint |
| CN109206889A (en) * | 2018-08-22 | 2019-01-15 | 扬中市红光金属制品有限公司 | A kind of wear-resisting animal ear tag and its processing technology |
| CN109369895B (en) * | 2018-09-15 | 2021-02-09 | 福建省南安市华龙树脂有限公司 | Unsaturated polyester resin for anti-freezing coating and preparation method thereof |
| CN114106617B (en) * | 2021-12-03 | 2022-05-10 | 清远市浩宇化工科技有限公司 | Putty for vehicles and preparation method and application thereof |
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| CN101235129A (en) * | 2008-03-05 | 2008-08-06 | 安徽大学 | Method for preparing polybutadiene-base water polyurethane and modified emulsion thereof |
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| JP特开2011-57771A 2011.03.24 |
| 崔锦峰 等.无溶剂常温固化不饱和聚酯聚氨酯涂料的研究.《中国建材科技》.2011,(第01期),第38-42页. * |
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